New fluorinated dienes and process for preparing same

ABSTRACT

Fluorinated dienes are disclosed which have the formula

United States Patent [1 1 Riess et al.

( 1 Aug. 26, 1975 l l NEW FLUORINATED DIENES AND PROCESS FOR PREPARINGSAME [75] Inventors: Jean G. Riess; Maurice LeBlanc;

Georges Santini; Jacky Guion, all of Nice, France Produits ChimiquesUgine Kuhlmann, Paris, France [22] Filed: Feb. 26, 1974 [2H Appl.New/1446,10!

[73] Assignee:

[30] Foreign Application Priority Data Feb 28, [973 France a. 73.07l07[52] U.S. Cl 260/6513; 260/6535; 260/653.l T [51] Int. Cl." C07: 21/18;C07c 2 H20; CO7c l7/28 [58] Field of Search 260/6533 653.l R, 653.] T,

[56] References Cited UNITED STATES PATENTS 2,996.527 8/!961 Krespan260/6533 Paciorck 260/6533 Haszeldinc 260/6533 Primary ExaminerD.Horwitz Attorney, Agent, or FirmPennie & Edmonds [57 I ABSTRACTFluorinated dienes are disclosed which have the formula 9 Claims, N0Drawings NEW FLUORINATED DIENES AND PROCESS FOR PREPARING SAMEDESCRIPTION OF THE INVENTION I. Field of the Invention This inventionrelates to fluorinated dienes and a method for their preparation.

II. Description of the Prior Art The compound tetrafluorobutadiene F,C=Cl-l CH =CF is known in the art but this compound does not fall withinthe framework of the present invention because R, and R substantiallydiffer from F.

K. L. Paciorak, B. A. Merkl and C. T. Lenk, in volume 27 of the JOURNALOF ORGANIC CHEMIS- TRY, page 1,015 (I962) describe the followingcompound:

3 c ca CF CZFS (In) CZFS Although the article describes a compound (III)which approaches the compound (I) of the claimed invention, it neithersuggests nor discloses the compounds (I).

The present invention involves the discovery that by reacting the twocompounds R CF I and R CF CH CH with copper in the presence of a solventaccording to the reaction:

A. R,-'CF I R CF. CH CH 2C Solvent/ one obtains a mixture of compounds(IV and I) R CF CH CH- CF R,"

and

R CF=CH -CH=CF R,-'

The initial reagents R CF l and Rp'CFg CH =CH are known (Hazeldine, J.CHEM. SOC, I949, page 2,856).

These compounds are extremely difficult to separate. The applicantshave, however, discovered that by varying the conditions of thereaction, it is possible to produce the compound (I) alone. This is anunexpected and surprising result.

The applicants have found that at relatively mild experimentalconditions, for example l5 hours at IC, a mixture of approximately 20%of the compound of the formula (IV) and 80% of the compound of theformula (I) resulted which was difficult to separate, However, when moresevere conditions, i.e., prolonged heating or higher temperature whereapplied, it was unexpectedly found that the compound of formula (I) wasobtained exclusively.

SUMMARY OF THE INVENTION The present invention involves compounds offluorinated dienes having the formula R CF =CH CH =CF R in which R, ""4are the same or different and each represents a fluorocarbon radicalcontaining 1 to 20 carbon atoms C F where n equals 1 to 20). Thecompounds which are the subject of the present invention are alsocapable of containing a few atoms of hydrogen or halogens other thanfluorine.

The method of preparation of the compounds of formula (I) can berepresented by the equation:

= CH-CH CF R,"

This reaction may be carried out at a temperature from about I20C toabout 150C for a period between about l0 hours to about 72 hours. Thereaction time may vary and is approximately inversely proportional tothe temperature. Some examples of solvents that can be used includedimethyl formamide (DMF), dimethyl sulphoxide (DMSO), an aromatic orheterocyclic amine such as pyridine. a heavy ether of the ethylenepolyoxide type, a glycol dimethyl ether (glyme or any other suitablesolvent.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The above reaction (B) containsan excess of approximately 5 to of the compound R 'CF- I above thestoichiometric quantity required and about 2 to 5 gram atoms of copperper mole of R 'CF I. The copper which can be used in the above reactionmay be, for example, copper produced by displacement reaction CuSO, Z ICu I ZnSO or copper produced via the reduction of CuO.

The reaction time and the temperature vary in inverse proportion. Forexample, for a temperature of C a reaction time of about 72 hours isnecessary, while at C the formation of the compound (I) in apreponderant quantity is observed after only about l0 hours.

Tetrafluorobutadiene may be prepared in accordance with the abovereaction (8) by reacting the compound of the formula HCF CH=CH= and thecompound CF l in a molar excess of approximately 5 to IOO%, in thepresence of approximately 2 to 5 gram atoms of copper per mole of thecompound CF ,l, in a solvent at a temperature of between about l20C andabout 150C for a time to produce exclusively or substantiallyexclusively tetrafluorobutadiene. Examples of solvents that may be usedare mentioned above.

The new compounds of the present invention can be used as monomers forhomopolymerization or copolymerization with fluorine dienes or withethylenically unsaturated hydrocarbons. such as propylene by standarddiene polymerization or copolymerization techniques in which latterinstance they may be used to form polymers (films, for example) withstain resistant properties.

In addition, the fluorinated diolefins of the invention have excellentphysical properties for use as oxygen transport in biological systems(i.e., synthetic blood and other uses). By way of illustration has adensity of 1.689 and at 37C under 760 mm Hg the above fluorinateddiolefin can dissolve 41.5 ml of oxygen per 100 ml and 222 ml of CO perl ml of the olefin.

Fluorocarbons have been recognized as having utility as blood substitutein animals. See, for example, the publication CHEMISTRY, Vol. 46(8).September I973. pp. 20 and 21.

The following examples illustrate the invention in a nonrestrictivemanner.

EXAMPLE 1 A mixture of C F CF I (0.062 moles) and C l CF CH CH (0.05moles) was heated with g of powdered copper produced via thedisplacement reaction of CuSO, with Zn, and 50 mls of anhydrous DMF at140C for about 72 hours. After extraction with ether and centrifuging soas to eliminate the copper salts formed, the reaction product was washedwith water so as to eliminate the DMF. The ether phase was then driedover magnesium sulphate and then evaporated. The residue was distilledunder reduced pressure. The compound C F CF=)\ CH-CH=CF-C,,F,, wasobtained in a yield of 80%.

Analysis C H F 9?. calculated for C,. .H.,F.,., 27.38 0.38 72.24 '4'found in reaction product 27.6l 0.45 7|.88

The compound obtained is liquid and distils at 38C under 0.5 mm Hg. Thecompound was identified by its nuclear magnetic resonance spectrum(NMR).

EXAMPLE 2 The procedure in Example 1 was followed except that the 0.05moles of C;,F CF CH CH was changed to 0.062 moles of C F CF l. Thisresulted in the formation of the compound C,,F-, CF CH CH CF C 1 in ayield of 75%.

Analysis C H F "/r, calculated for C ,H.,F- 26.84 0.32 72.84 64 found inthe reaction product 27.04 0.35 72.5l

The compound obtained is a liquid which distils at 54C under 0.4 mm Hg.The compound was identified by its NMR spectrum.

EXAMPLE 3 The mixture of Example I was heated to 150C in DMF. Thepercent conversion into the desired compound C F CF= CH CH CF C,,F equalto 75% after about 18 hours. In DMSO the percent of conversion is equalto 70% after about l8 hours.

EXAMPLES 4 to 7 By repeating the conditions of Example l, the followingcompounds were prepared:

These compounds are identifiable by their distillation temperaturesunder reduced pressure and/or their melting point as indicated above, aswell as by their NMR spectra.

We claim:

1. Compounds of the formula in which R and R," are the same or differentand each represents a fluorocarbon radical containing one to 20 carbonatoms.

2. Compounds of the formula according to claim 1 wherein thefluorocarbon radical contains a small amount of hydrogen atoms and ahalogen atom other than fluorine.

3. A process for the preparation of the compounds according to claim 1,which comprises reacting a compound of the formula R, CF CH CH, and acompound of the formula R,.-' CF l in molar excess of approximately 5 towherein R, and R,-' are the same or different and each represents afluorocarbon radical containing one to 20 carbon atoms, in the presenceof approximately 2 to 5 gram atoms of copper per mole of the compound R'CF l and in a solvent at a temperature between about I20C and 150C fora period of time to produce exclusively or substantially exclusively thecompounds of formula I.

4. A process for the preparation of the compounds according to claim I,which comprises reacting a compound of the formula R CF CH CH and acompound of the formula R," CF -l in molar excess of approximately 5 tol00%, wherein R, and R are different and each represents a fluorocarbonradical containing one to 20 carbon atoms, in the presence ofapproximately 2 to 5 gram atoms of copper per mole of the compound R 'CFl in a solvent at a temperature between about C and C for a period oftime to produce exclusively or substantially exclusively the compoundsof formula I.

5. A process according to claim 3 wherein the solvent is selected fromthe group consisting essentially of dimethylformamide, dimethylsulphoxide, heavy ethers, glycol dimethyl ether (glyme), aromatic aminesand heterocyclic amines.

6. A process according to claim 4 wherein the solvent is selected fromthe group consisting essentially of dimethylformamide. dimethylsulphoxide, heavy ethers. glycol dimethyl ether (glyme), aromatic aminesand heterocyclic amines.

7. A process for the preparation of compounds having the formula lll inwhich R and R are the same or different and represent a fluorine atom ora fluorocarbon radical containing one to carbon atoms by reacting acompound of the formula R -CH -CH=CH and a compound of the formula RyCFzl in molar excess of approximately 5 to 100% in the presence ofapproximately 2 to 5 gram atoms of copper per mole of Rp CFgl in asolvent at a temperature above about 120C for a time sufficient toproduce exclusively or substantially exclusively the compound of formula1.

8. A process for the preparation of tetrafluorobutadiene, whichcomprises reacting the compound of the heterocyclic amines.

UNITED STATES PATENT AND TRADEMARK OFFICE PATENT NO.

DATED INVENTOR(S) CERTIFICATE OF CORRECTION it is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Column,2, line 1, "R CF=CHCH=CF-R should read Column delete Columndelete Column delete Column delete Column delete Column [SEAL] line 23,"C F -CF=lCHCH=CFC F should line 5, "C3F7-CF=CH-CH= \CF-C3F7" should "CF CF= \CHCH=CFC5F1 should line 7, "C7F 5CF=}\CH-CH=CF-C5F should line 8,"C F CF=ACH-CH=CFC F should line 66, "FF" should read R Arrest:

RUTH C. MASON Arresting Officer C. MARSHALL DANN (mnmrssiunvr uj'ParenIsand Trademurks

1. COMPOUNDS OF THE FORMULA
 2. Compounds of the formula according toclaim 1 wherein the fluorocarbon radical contains a small amount ofhydrogen atoms and a halogen atom other than fluorine.
 3. A PROCESS FORTHE PREPARATION OF THE COMPOUNDS ACCORDING TO CLAIM 1, WHICH COMPRISESREACTING A COMPOUND OF THE FORMULA RF - CF2 CH = CH2 AND A COMPOUND OFTHE FORMULA RF'' CF2 - 1 IN MOLAR EXCESS OF APPROXIMATELY 5 TO 100%,WHEREIN RF AND RF'' ARE THE SAME OR DIFFERENT AND EACH REPRESENTS AFLUOROCARBON RADICAL CONTAINING ONE TO 20 CARBON ATOMS, IN THE PRESENCEOF APPROXIMATELY 2 TO 5 GRAM ATOMS OF COPPER PER MOLE OF THE COMPOUNDRF'' CH2 - 1 AND IN A SOLVENT AT A TEMPERATURE BETWEEN ABOUT 120*C AND150*C FOR A PERIOD OF TIME TO PRODUCE EXCLUSIVELY OR SUBSTANTIALLYEXCLUSIVELY THE COMPOUNDS OF FORMULA
 1. 4. A process for the preparationof the compounds according to claim 1, which comprises reaCting acompound of the formula RF -CF2 - CH CH2 and a compound of the formulaRF'' CF2- I in molar excess of approximately 5 to 100%, wherein RF andRF'' are different and each represents a fluorocarbon radical containingone to 20 carbon atoms, in the presence of approximately 2 to 5 gramatoms of copper per mole of the compound RF''CF2 - I in a solvent at atemperature between about 120*C and 150*C for a period of time toproduce exclusively or substantially exclusively the compounds offormula I.
 5. A process according to claim 3 wherein the solvent isselected from the group consisting essentially of dimethylformamide,dimethyl sulphoxide, heavy ethers, glycol dimethyl ether (glyme),aromatic amines and heterocyclic amines.
 6. A process according to claim4 wherein the solvent is selected from the group consisting essentiallyof dimethylformamide, dimethyl sulphoxide, heavy ethers, glycol dimethylether (glyme), aromatic amines and heterocyclic amines.
 7. A process forthe preparation of compounds having the formula F F - CF CH - CH CF -RF'' (I) in which RF and RF'' are the same or different and represent afluorine atom or a fluorocarbon radical containing one to 20 carbonatoms by reacting a compound of the formula RF- CH2-CH CH2 and acompound of the formula RF''CF2I in molar excess of approximately 5 to100% in the presence of approximately 2 to 5 gram atoms of copper permole of RF''CF2I in a solvent at a temperature above about 120*C for atime sufficient to produce exclusively or substantially exclusively thecompound of formula I.
 8. A PROCESS FOR THE PREPARATION OFTETRAFLUOROBUTADIENE, WHICH COMPRISES REACTING THE COMPOUND OF THEFORMULA H CF2 -CH = CH2 AND THE COMPOUND CF31 IN A MOLAR EXCESS OFAPPROXIMATELY 5 TO 100%, IN THE PRESENCE OF APPROXIMATELY 2 TO 5 GRAMATOMS OF COPPER PER MOLE OF THE COMPOUND CF31, IN A SOLVENT AT ATEMPERATURE OF BETWEEN ABOUT 120*C AND ABOUT 150*C FOR A TIME TO PRODUCEEXCLUSIVELY OR SUBSTANTIALLY EXCLUSIVELY TETRAFLUOROBUTADIENE.
 9. Aprocess according to claim 8 wherein the solvent is selected from thegroup consisting essentially of dimethylformamide, dimethyl sulphoxide,heavy ethers, glycol dimethyl ether (glyme), aromatic amines andheterocyclic amines.